WO2014178543A1

WO2014178543A1 - Effective operation of circulating fluidized bed for preparing light olefins from methanol through real time monitoring of intermediates

Info

Publication number: WO2014178543A1
Application number: PCT/KR2014/002926
Authority: WO
Inventors: 김주완; 채호정; 정광은; 김태완; 김철웅; 정순용
Original assignee: 한국화학연구원
Priority date: 2013-05-01
Filing date: 2014-04-04
Publication date: 2014-11-06
Also published as: KR101494229B1; KR20140130603A

Abstract

The present invention relates to an effective operation of a circulating fluidized bed for preparing light olefins from methanol by monitoring the selectivity of intermediates, and specifically, to a method for predicting the extent of inactivation of a used catalyst by monitoring the selectivity of dimethyl ether (DME) and maintaining the optimized coke level by controlling the flux of air for catalyst regeneration, thereby effectively enhancing the productivity of a light olefin-based hydrocarbon, and particularly, maintaining the remarkable selectivity for ethylene and propylene.

Description

【Specification】

[Name of invention]

Efficient Operation of a Circulating Fluidized Bed Process for the Production of Light Olefins from Methane with Real-time Monitoring of Intermediates ^''

[Technical Field]

The present invention relates to an efficient operation of a circulating fluidized bed process for preparing light olefins from methane through monitoring the selectivity of intermediates. Specifically, the degree of deactivation of the catalyst used by monitoring the selectivity of dimethyl ether (DME) By predicting the efficiency of the catalyst and maintaining the optimized coke level by adjusting the air flow rate for catalyst regeneration, the present invention relates to a method for effectively increasing the productivity of light olefin hydrocarbons and, in particular, maintaining excellent selectivity to ethylene and propylene.

<2>

BACKGROUND OF THE INVENTION _.

Light olefins are ethylene, propylene, and butenes obtained by naphtha cracking, and are the basic raw materials for the petrochemical industry, which are essential for the manufacture of various chemical products such as synthetic resins, synthetic rubbers, and alcohols. Recently, some of the light olefins are also produced in the ethanol pyrolysis process or the fluidized bed catalytic cracking process, but the production scale is much smaller than that of naphtha.

<4>

<5> The naphtha pyrolysis process uses a lot of energy to use about 40% of the energy used in petrochemical plants, but it is widely used because of its simple process and easy operation. However, due to the sharp rise in the price of crude oil, the price of naphtha, a raw material, has risen, and the cost burden of the energy required for the pyrolysis process increases, and various alternative processes are being developed.In addition, to reduce the huge amount of carbon dioxide emitted during energy production, The development of a process to produce light olefins using less energy from the resources of the company is very urgent.

<6>

Recently, much research has been conducted on a circulating fluidized bed process for manufacturing light olefins (methano 卜 to-olefin, ΜΤ0) from methanol as a process to replace naphtha pyrolysis to prepare light olefins. Specifically, in the MTO reaction, methanol is dehydrated in an acid catalyst to be an intermediate product, dimethyl ether, followed by conversion of light ethylene, propylene, butene and the like into lepin, and the converted light olefin is polymerized, cyclized, dehydrogenated, etc. female The reaction then yields branched saturated and aromatic hydrocarbons.

<8>

Therefore, in the MT0 reaction, it is a major task to maximize the goodness of light olefins by promoting the production of light olefins and suppressing the addition reaction of light olefins, and many studies have been reported to solve the above problems. It has been done.

<10>-

Conventional Patent Document 1 (US Pat. No. 4,873,390) discloses carbon on a catalyst that returns from contacting the catalyst with a regeneration medium to recontacting the regenerated catalyst with various oxygenates as reactants. By controlling the amount of vaginal deposits, there is proposed a method for increasing the amount of ethylene and propylene produced by catalytic conversion of oxygenated compounds such as methanol in a fluidized bed reaction system.

<12>

In addition, Patent Document 2 (US Pat. No. 6,166, 282) is a process type for preparing olefins from oxygenated compounds, which can reduce the amount of bed residue of a catalyst compared to a conventional bubbling bed. It is proposed a fast fluidized bed reaction process that can reduce the size, and especially in the fast fluidized bed process for producing light olefins, the conversion of olefins is greatly influenced by reaction variables such as temperature, catalyst activity, and space velocity. Doing.

<14>

<15> Further, Patent Document 3 (US Pat. No. 5, 952, 538) presents the effect of the space velocity on the olefin selectivity and the optimum range of space velocity among the process variables in the conversion of oxygenated compounds to elefin. Doing.

<16>

In addition, Patent Document 4 (U.S. Patent No. 6,023,005) discloses that maintaining the average coke content at a level in the process of producing light olefins from methane increases the selectivity of light olefins. It is reported to affect.

<18>

<19> Furthermore, in the non-patent document KFuel Processing Technology, 88 (2009) 437-441)

Guozhen Qi et al. Reported that olefin selectivity varies greatly with the coke content in the process of producing light olefins from methanol, and the coke content depends on the space velocity and reaction temperature.

<20> Through the preceding studies, it can be seen that the coke content plays a very important role in the coarse I and hard water of hard lepin. Therefore, in the circulating fluidized bed reaction process for preparing light olefins from oxygenated compounds, optimization of the regeneration process of catalysts deactivated by coking (carbon deposition) is very important to increase the yield of light olefins and improve selectivity.

<22>

<23>^"conversion ratio of the reaction product, if completely reproduce the catalyst used for the production of light olefins is high but ethylene, is the yield of light olefins decreases and propylene, the reproduction is insufficient to open if the coke on the catalyst remains much neobu has In addition to lowering the yield as a whole, the conversion of the reactants is also lowered, which is a problem, so it is very important to operate stably with an optimum degree of regeneration.

<24>

However, until now, some of the catalyst after reaction has been recovered to determine the degree of coke of the catalyst through the coke content analysis, and accordingly, a method of adjusting the reaction conditions (space velocity and reaction temperature) has been used. Through the process of collecting catalyst sample, catalytic thermal analysis, catalytic coke content analysis, process reaction condition control, response time from analysis of coke content and control of process variables is long, so There is a problem that it is difficult to adjust effectively.

<26>

Therefore, the present inventors have been interested in the efficient operation of the circulating fluidized bed process for producing hard lephine from methane, and the selectivity of the intermediate product dimethyl ether and the coke content of the catalyst in the light olefin conversion reaction. To predict the deactivation rate of the catalyst by monitoring the selectivity of dimethyl ether, and to improve the yield of hardpin by effectively maintaining the optimum coke content by adjusting the air flow rate for catalyst regeneration. In particular, it was confirmed that there is an effect that can maintain excellent selectivity to ethylene and propylene, and completed the present invention.

<28>

[Detailed Description of the Invention]

[Technical problem]

An object of the present invention is to provide a method for predicting the deactivation of the catalyst used by monitoring the selectivity of the intermediate dimethyl ether in preparing light olefins from methanol. <30>

In addition, an object of the present invention is a catalyst regenerated to improve the yield of light olefins and especially the selectivity of ethylene and propylene by monitoring the selectivity of intermediate dimethyl ether in preparing light olefins from methanol. It is to provide a method for preparing a hard lepin that can optimize the coke content of.

<32>

Furthermore, the present invention aims to monitor the selectivity of the dimethyl ether as an extra product in the production of light olefins from methanol to optimize the yield of light olefins and in particular the selection of ethylene and propylene by optimizing the coke content of the regenerated catalyst. It is to provide a method for improving the degree.

<34>

[Technical Solution]

In order to achieve the above object, the present invention

Contacting the methanol supercatalyst in a circulating fluidized bed reactor having a catalyst regeneration unit and a product separation unit to produce light olefins (step 1); And

<37>. Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step

2); provides a method for predicting the deactivation of the catalyst used to prepare light olefins.

<38>

In addition, the present invention

Preparing light olefins by contacting methanol with the catalyst in a circulating fluidized bed reactor equipped with a catalyst regeneration unit and a product separation unit (step 1);

Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step

2); And

Injecting air for regeneration of the catalyst by separating the used catalyst of step 1,

Extruding the injected air flow rate according to the selectivity of the dimethyl ether of step 2 (step 3); It provides a method for producing a light olefin comprising a.

<44>

Furthermore, the present invention

Methanol in a circulating fluidized bed reactor with catalyst regeneration and product separation

^' Contacting the catalyst with a catalyst to produce light olefins (step 1);

Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step 2); And

In order to regenerate the catalyst by separating the used catalyst of step 1,

Step K) to adjust the injected air flow rate according to the selectivity of the dimethyl ether of step 2; It provides a method for improving the yield of light olefin comprising a.

<50>

Advantageous Effects

According to the present invention, in the process of producing hard lepine from methane and other oxygen-containing compounds by using a circulating fluidized bed process, a correlation analysis with the selectivity of dimethyl ether, which is an intermediate product produced after the reaction, is performed. Thus, the deactivation of the catalyst (coke level) can be predicted in real time.

_{_<52>} Further, according to the present invention is to control the air flow rate for catalyst regeneration by real-time monitoring of the selectivity of the ether, by maintaining the degree of optimum coke, and can increase the yield of light oleic hydrocarbon effectively, particularly ethylene And it has the effect of maintaining excellent selectivity for propylene.

<53>

[Brief Description of Drawings]

1 is a schematic diagram of a circulating fluidized bed reaction vessel having a catalyst regeneration unit and a product separation unit according to an embodiment of the present invention.

<56> [Description of the Sign]

1 ： riser

<58> 2: stripper _. (stripper)

3: regenerator ''

4 ： stripper slide valve

<6i> 5: Regenerator slide valve

6: stripper transfer line

7: regenerator transfer line

8: flue gas control valve

9 ： product gas control valve

10: regenerator air inlet

11: methanol feed inlet

12: riser nitrogen inlet line (riser nitrogen inlet)

13 ： stripper nitrogen inlet 14: flue gas outlet

15: product gas outlet

[Best form for implementation of the invention]

The present invention relates to an efficient operation of a circulating fluidized bed process for preparing light olefins from methanol through monitoring the selectivity of intermediates, specifically, dimethyl ether.

(DME) selectivity can be monitored to predict the degree of deactivation of the catalyst used and to control the air flow for catalyst regeneration to maintain the optimum coke level, effectively increasing the productivity of light olefin hydrocarbons, especially ethylene and propylene The present invention relates to a method capable of maintaining excellent selectivity to.

<74>

Hereinafter, the present invention will be described in detail.

<76>

First, the present invention

Contacting methanol with the catalyst in a circulating fluidized bed reactor having a catalyst regeneration unit and a product separation unit to produce light olefins (step 1); And

Monitoring the selectivity of the dimethyl ether which is the intermediate product of step 1 (step

2); It provides a method for predicting the deactivation of the catalyst used in the preparation of hard olepin.

<80>

Hereinafter, the method for predicting the deactivation of the catalyst used in the preparation of hard lepin according to the present invention will be described in more detail in each step.

<82>

First, in the method for predicting the deactivation of the catalyst used in the preparation of light leulev according to the present invention, step 1 is contacted with methanol in a circulating fluidized bed reactor equipped with a catalyst regeneration unit and a product separation unit. It is a step to prepare a hard olepin.

<84>

Specifically, a schematic diagram of the circulating fluidized bed reactor having the catalyst regeneration part and the product separation part of step 1 is shown in FIG. 1.

<86>

Referring to Figure 1, when explaining the step of manufacturing a hard relefin by the circulating fluidized bed reactor of step 1, vaporized methane is injected into the riser (1) through the methanol injection line (11), Quality injected through riser nitrogen injection line 12 to ascend the catalyst . It is injected into the ascension tube 1 together with the cow. In the riser (1), the reaction proceeds between the circulating catalyst and the methane introduced from the bottom.

Next, the effluent passing through the riser 1 flows into the stripper 3, where the catalyst and the product gas are separated. In the lower part of the stripper 3, volatile hydrocarbons are recovered by the contact of the catalyst with nitrogen, and the catalyst separated in the stripper 3 is sent to the regenerator 2. In the regenerator 2, the catalyst is regenerated by contact of the catalyst with air. The regenerated catalyst in the regenerator is transferred to the bottom of the riser and reacted with methanol again in the riser. In the circulating fluidized bed reactor, the circulation of the catalyst and the reaction of methanol proceed continuously and repeatedly.

<89>

Next, in the method for predicting the deactivation of the catalyst used to prepare the light olefin according to the present invention, step 2 is monitoring the selectivity of the dimethyl ether which is the intermediate product of step 1.

<91>

Specifically, the suntec degree of dimethyl ether, which is the intermediate product of step 2, is performed through reaction product analysis, for example, gas chromatography analysis. In the MT0 reaction, methane is dehydrated in this acid catalyst to be an intermediate product, dimethyl ether, and then converted into light olefins such as ethylene, propylene, butene, and the like. The converted light olefins undergo various reactions such as polymerization, ring polymerization, and dehydrogenation. For example, since it is a saturated hydrocarbon of d-C ₃ and hydrocarbon of C _{5 or} more, the reaction product may be dimethyl ether, ethylene, propylene, butene, saturated hydrocarbon of -C ₃ , hydrocarbon of C ₅ or more, and the like. have.

<93>

According to the method for predicting the deactivation of the catalyst used in the production of light olefins of the present invention, in the production of light lepin from methane using a circulating fluidized bed process, the deactivation of the catalyst used, i.e., deposited on the catalyst The coke content can be predicted in real time through the correlation analysis with the selectivity of the dimethyl ether, which is the extra product.

<95>

In the production of light olefins from methanol using a circulating fluidized bed process, the activity of the catalyst, i.e. the coke content deposited on the catalyst, is an important parameter in improving the yield of light olefins, in particular the selectivity of ethylene propylene, For this purpose, it is very important to optimize the regeneration process, which is deactivated by carbon deposition. <98>. Conventionally, in order to confirm the coke content deposited on the catalyst

After recovering and confirming the degree of coke of the catalyst, a method of controlling the reaction conditions (space velocity, reaction temperature) is used accordingly. In this case, the catalyst sample, catalyst thermal analysis, catalyst coke content analysis, process reaction conditions Because of the process of adjustment, it is difficult to adjust the coke content quickly and effectively because the response time to analysis of the coke content and the adjustment of the process variables becomes long.

<99>

On the other hand, according to the method for predicting the deactivation of the catalyst used in the production of light olefins of the present invention, methane is analyzed in real time by gas chromatography (within 20 minutes), and dimethyl ether (DME By monitoring the selectivity of), it is possible to effectively analyze the degree of deactivation of the catalyst and to significantly reduce the step speed of the light olefin production process from methanol maintaining a certain level of coke. .

: 101>. .

102> In addition, the present invention

Contacting methane with a supercatalyst in a circulating fluidized bed reactor having a catalyst regeneration section and a product separation section to produce light olefins (step 1);

Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step

2); and

105> separate the spent catalyst from step 1 and inject air for regeneration and

Adjusting the flow rate of the injected air according to the selectivity of the dimethyl ether of step 2 (step 3); It provides a method for producing a light olefin comprising a.

107>

108> Hereinafter, a method for preparing hard olepin according to the present invention will be described in more detail at each step. ᅳ

109>

First, step 1 and step 2 in the method for preparing light olefins according to the present invention may be carried out in the same manner as described in the method for predicting the deactivation of the catalyst used for the production of light olefins.

111>

ii2> Specifically, the catalyst of step 1 is not particularly limited in the case of a catalyst generally used in the MT0 reaction, for example, a silicoaluminophosphate system. (silicoaluminophosphate, SAPO) or zeolites (zeol ite) can be selected to ⁰ ¾ ^μ , preferably SAPO-34, SAP0-18 or ZSM-5 can be selected and used. ᅳ Next, in the method for preparing light olefin according to the present invention, step 3 is to inject air for regeneration of the catalyst by separating the used catalyst of step 1, the injected air flow rate to selectivity of the dimethyl ether of step 2 According to the steps to adjust. Specifically, the air flow rate injected for the catalyst reassembly of step 2 may be adjusted to maintain the dimethyl selectivity at '0.2-10.5 ¾', more preferably at 0.5-8.1%. If the flow rate of the air injected for the catalyst regeneration is injected such that the dimethyl selectivity is less than 0.2%, there is a problem that the selectivity of ethylene is significantly lowered, and when it is injected to be maintained above 10.5%, light olefins (ethylene, propylene ) Selectivity and methane conversion rate is low, it is good to maintain the above range. In addition, the air flow rate injected for the regeneration of the catalyst of step 2 is preferably adjusted so that the average coke content of the regenerated catalyst is 0.2-5.9 weight ¾>, more preferably 0.5-4.6 weight ¾. If the flow rate of air injected for regenerating the catalyst is injected such that the average coke content of the regenerated catalyst is less than 0.2 wt%, there is a problem that the ethylene selectivity is significantly lowered, and if it is injected more than 5.9 wt%, it is hard. There is a problem that the selectivity of olefins (ethylene, propylene) and methanol conversion are lowered, and it is better to maintain the range of addition. Furthermore, the temperature of the reaction vessel is 300 V-600 ^° C, the circulation rate of the catalyst in the reactor is 1-100 kg / h, the space velocity of the methane injected into the reactor is 0.5-300 h ^"1 If the reaction temperature is less than 300 V, the conversion of methanol is lowered and secondary dehydration does not occur, so dimethyl ether is mainly produced, resulting in a significantly lower harden selectivity. There is a problem that the deactivation rate of the catalyst is increased rapidly, and it is preferable to maintain the temperature range. If the circulation rate of the catalyst at less than lkg / h is a problem that the fluidity of the catalyst in which the circulating fluidized bed reaction is slowly developed, and the catalyst residence time in the catalyst regenerator is greatly increased if it is more than 100 kg / h There is a problem that the reduced regeneration does not occur, it is preferable to maintain the circulation rate. In addition, when the space velocity of methanol injected into the reactor is less than 0.5 h ¹ , the throughput of methane is very low, making it difficult to secure economic productivity, and when it exceeds 300 h ¹ , the conversion rate of the catalytic reaction is greatly reduced. It is good to maintain the space velocity.

: 123> ^■

In addition, it is preferable that the temperature of the catalyst regenerator is 500-700 ^° C, and the air flow rate injected for regenerating the catalyst is 5-50 1 / min.

125>

126> If the temperature of the catalyst regenerator is less than 500 ^° C, there is a problem that regeneration of the deposited coke is not performed, and if the temperature of the catalyst regenerator is higher than 700 ^° C, the catalyst crystal structure collapses, so that the temperature is maintained within the above range. good. In addition, when the flow rate of air injected for catalyst regeneration is less than 5 1 / min, there is a problem that the catalyst is not sufficiently regenerated, and if it is more than 50 1 / min, there is a problem that can not maintain the coke state of the catalyst is not preferable.

127>

128> Furthermore, the present invention

Contacting methanol with the catalyst in a circulating fluidized bed reactor having a catalyst regeneration unit and a product separation unit to produce light olefins (step 1);

130> Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step

2); and

131> separate the catalyst used in step 1 and inject air for regeneration of the catalyst,

Adjusting the injected air flow rate according to the selectivity of the dimethyl ether of step 2 (step 3); It provides a method for improving the yield of light olefin comprising a.

133>

Specifically, in the method for improving the yield of hard leucine according to the present invention, steps 1 to 3 may be performed in the same manner as described in the method for preparing the hard leucine.

135>

136> Method for producing light olefins or improving the yield of light olefins according to the present invention According to the present invention, the selectivity of the intermediate dimethyl ether is monitored in real time to adjust the air flow rate for the rearing of the corpus, maintaining the optimum coke level, thereby effectively increasing the productivity of the light olefin hydrocarbons. Has the effect of maintaining excellent selectivity for

: 137>

[Form for implementation of invention]

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are merely to illustrate the invention, the content is not limited by the following examples.

: 139>

Example> Circulating fluidized bed process for the production of light olefins from methane through real-time monitoring of intermediate products

141> The catalyst used in the examples of the present invention is a micro-spherical SAP0-34 molding catalyst,

The SAP0-34 powder, alumina sol, and Karlan binder were uniformly mixed under acidic conditions, and then spray dried to form. The average density of the shaped catalyst is 670 kg / m ³ , the wear rate is 4.5%, the particle size is within 53-200.

142>

In addition, the methanol used in the present embodiment is vaporized through a preheater at a flow rate of 604 g / h, and the vaporized methanol has an internal diameter with nitrogen introduced at a flow rate of 6 L / min for the catalyst to rise. It enters the bottom of the riser at 14.24 画 and 4 m in height. In the riser, the catalyst circulated at a rate of 30 kg / h and methanol flowing from the bottom meet and the reaction proceeds. The temperature of the riser is maintained at 420 ^° C by the heater.

144>

Next, the effluent, which has passed through the chamber, flows to the stripper, where the catalyst and product gas are separated. Under the stripper, volatile hydrocarbons are recovered by contact of the catalyst with nitrogen, and the catalyst separated from the stripper is sent to the regenerator. In the regenerator, the catalyst is regenerated by contact of the catalyst with air, and the regenerator's silver is maintained at 600 ^° C by the heater. The rate of inflow of air into the regenerator is controlled by the degree of coke and olefin selectivity distribution of the regenerated catalyst.

146>

The catalyst regenerated in the regenerator is then transferred to the bottom of the riser, which again reacts with methane. In a circulating fluidized bed reaction, the circulation of the catalyst and the reaction of methane proceed continuously and repeatedly. The product gas separated from the stripper is gas Olefin selectivity and methanol conversion are analyzed by chromatography. Carbon monoxide, carbon dioxide, and oxygen components of the flue-gases discharged from the regenerator are analyzed by a gas analyzer, and the flow rate of the flue-gases is analyzed by a dry flow meter. In addition, the coke content of the catalyst is measured by extracting the catalyst from the bottom of the regenerator and stripper.

: 148>

In the same reaction conditions as the above-mentioned process, only the amount of regenerator inlet air was changed to monitor the dimethyl ether selectivity accordingly.

150>

151> <Example 1> Dimethel ether selectivity monitoring according to the amount of regenerator inlet air-1

In order to remove all of the arsenic deposited on the catalyst, the regenerator air flow was injected at 15.5 L / min to prevent the formation of dimethyl ether.

153>

154> <Example 2> Dimethel ether selectivity monitoring according to the amount of regenerator inlet air-2

The air flow rate of the regenerator was injected at 12 L / min to maintain the selectivity of dimethyl ether at 0.2%.

156>

157> <Example 3> Dimethel ether selectivity monitoring according to the regenerator intake air volume-3

The air flow rate of the regenerator was injected at 11.8 L / min to maintain the selectivity of dimethyl ether at 1.2%.

159>

160> <Example 4> Dimethel ether selectivity monitoring according to the regenerator intake air volume-4

161> Inject the air flow rate of the regenerator at 11.6 L / min to improve the selectivity of dimethyl ether.

Maintained at 2.8%.

162>

163> <Example 5> Dimethel ether selectivity monitoring according to the regenerator intake air volume-5

164> Air flow rate of regenerator 기 11.4 L / min is injected to increase the selectivity of dimethyl ether.

Kept at 8.1%.

165>

166> <Example 6> Dimethel ether selectivity monitoring according to the regenerator intake air volume-6

167> The selectivity of dimethyl ether was increased by injecting air flow rate of regenerator at 11.0 L / min.

Kept at 10.5%.

168> <Experimental Example> Experimental Results of Circulating Fluidized Bed for Production of Light Lephine from Methanol> Examples 1 to 6 above were controlled by adjusting the inflow air flow rate of the regenerator in order to maintain the selectivity of the dimethyl ether contained in the product gas. will be. According to the experiment results in Table 1, before and after the MT0 reaction, the coke degree of the catalyst and the product selectivity distribution were used to maintain the coke degree of the catalyst at a constant level, thereby effectively increasing the yield of hard lephine hydrocarbons. The effect of the present invention, which enhances and particularly maintains good selectivity to ethylene and propylene, is described.

>^'

Table 1.

Experimental Results of Circulating Fluidized Bed for the Production of Light Olefin from Methanol

Example 1 is a thorough injection of the regenerator inlet air flow rate for complete regeneration of the catalyst, while the methanol conversion rate is reduced while the dimethyl ether selectivity is maintained at 0%.

99.5 ¾>, ethylene. The selectivity of propylene and butene was 14.2%, 41.0% and 14.3 ¾>, respectively. In the conversion of methanol to light olefins, depolymerization of the intermediate derivatives mainly leads to the dehydration reaction on the surface of the catalyst, resulting in the generation of saturated hydrocarbons and C ₅ or more hydrocarbons, resulting in very low total light olefin selectivity. >

> Example 2 shows that the regenerator air inflow is reduced compared to Example 1, even though the selectivity of dimethyl ether is maintained at 0.2%. The increased selectivity of dimethyl ether results in partial coke formation on the catalyst surface, resulting in deactivation of the catalyst. It means what started. The degree of coke of the regenerator outflow catalyst was 0.2%, and the degree of coke of the stripper effluent catalyst was 1.9%, which is 0.2-0.6% higher than that of Example 1. Ethylene selectivity compared with Example 1 by maintaining a certain amount of coke on the basis of the selectivity of dimethyl ether It was increased to 17.1%, and selectivity of propylene and butene was 40.9% and 13.4%, respectively. In addition, it was found that the conversion rate of methane did not show a great decrease to 99.7%. Example 3 reduced the regenerator air inflow from Example 2 so that the selectivity of dimethyl ether was maintained at 1.2%, the degree of coke of the regenerator effluent catalyst was 2.2%, and the degree of coke of the stripper effluent catalyst was maintained at 4.9%. It can be seen that an increase of 2-3% compared to Example 2. In addition, the increased coke content is the leupin formation reaction intermediate derived inside the catalyst micropore, and as a result, ethylene selectivity was greatly increased to 42.5% compared to Example 2, and propylene and butene and selectivity were 40.3%, respectively. %, 5.9%. In addition, the methanol conversion was 99.3%, showing no significant decrease. Example 4 reduced the regenerator air inflow from Experimental Example 3 so that the selectivity of dimethyl ether was maintained at 2.8 ¾, and the coke degree of the regenerator effluent catalyst was 3.1% and the coke degree of the stripper effluent catalyst was 5.2%. Coke content could be maintained, ethylene selectivity increased to 43.0% additionally, and propylene and butene selectivity were 40.1% and 5.4%, respectively. In addition, the methane conversion was 99.0%. Example 5 reduced the regenerator air inflow from Example 4 so that the selectivity of dimethyl ether was maintained at 8.1%, and the degree of coke of the regenerator outflow catalyst was 4.6Λ, which was 4.4% higher than that of Example 2. As a result, both ethylene and propylene selectivity was 39.3%, which was lower than those of Examples 3 and 4. In addition, the high coke content, the methanol exchange rate is also lowered to 97%. In Example 6, the selectivity of dimethyl ether was maintained at 10.5%, and the inlet regenerator air inflow amount was reduced from Experimental Example 5, and the coke degree of the regenerator effluent catalyst was 5.9%, which was 5.7 higher than that in Example 2. As a result, ethylene and propylene selectivity was 35.6% and 38.1%, respectively. In addition, it can be seen that the high coke content lowers the methanol conversion to 93.7%. From the above experimental results, the optimization of the coke content of the catalyst through the control of the degree of regeneration of the used catalyst is very important for improving the yield of hard lepin, and because the coke content and dimethyl ether are correlated, the regeneration degree is selected from dimethyl ether. Monitoring the road You can see that it can be adjusted.

<187>

Comparative Example Analyzing Coke Deposition by Directly Recovering Catalyst

Conventionally, a circulating fluidized bed process for producing hard olephine was operated by directly diluting a catalyst and analyzing a coke deposition amount. Specifically, since the coke content of the catalyst plays a very important role in the control of the olefin fin selectivity, the catalyst before and after the reaction is partially recovered from the regenerator and the lower part of the stripper, and the coke content is analyzed to confirm the degree of coke. Space velocity, reaction temperature, regenerator airflow). The coke content analysis of the catalyst uses thermal analysis methods such as thermal gravimetric analysis (TGA) / differential thermal analysis (DTA) and generally takes more than 8 hours, including sample pretreatment. do.

Therefore, the conventional methods undergo catalyst sampling, catalyst thermal analysis, catalyst coke content analysis, and process reaction condition control, and the response time to analysis of coke content and control of process variables becomes long. Coke content is difficult to control quickly and effectively.

(191>

On the other hand, according to the present invention, as described in the above examples and experiments, the product of methanol conversion reaction was analyzed in real time by gas chromatography (within 20 minutes), and dimethyl ether (DME) selectivity monitoring. By doing so, there is an advantageous effect of analyzing the degree of deactivation of the catalyst and significantly reducing the response speed of the light olefin production process from methane, which maintains the level of coke.

Claims

[Range of request]

[Claim 1]

Contacting the methanol supercatalyst in a circulating fluidized bed reaction vessel having a catalyst regeneration portion and a product separation portion to prepare a hard elephine (step 1); And

Monitoring the selectivity of the dimethyl ether which is the intermediate product of step 1 (step 2);

[Claim 2]

The method of claim 1,

The deactivation of the catalyst is a carbon coking of the catalyst used.

[Claim 3]

Preparing light olefins by contacting methanol with a catalyst in a circulating fluidized bed reactor having a catalyst regeneration unit and a product separation unit (step 1);

Monitoring the selectivity of dimethyl ether, an intermediate of step 1 (step

2); and

Separating the used catalyst of step 1 and injecting air for regeneration of the catalyst, and adjusting the injected air flow rate according to the selectivity of the dimethyl ether of step 2 (step 3); Method for producing a hard olepin comprising a.

[Claim 4]

The method of claim 3

The catalyst of step 1 is a silicoaluminophosphate system (silicoaluminophosphate, SAP0) or zeolite system (zeolite), characterized in that the preparation of hard elepin.

[Claim 5] _.

The method of claim 3,

The process for producing light olefins, characterized in that the air flow injected for the catalyst regeneration of step 2 is adjusted to maintain the selectivity of dimethyl ether at 0.2-10.5%.

[Claim 6]

The method of claim 3,

Air flow injected for the catalyst regeneration of step 2 is a method for producing light olefins, characterized in that the dimethyl ether selectivity is maintained to be maintained at 0.5-8.1%.

[Claim 7]

The method of claim 3, wherein

Air flow injected for the catalyst regeneration of step 2 is a method for producing a light olefin, characterized in that the average coke content of the regenerated catalyst is adjusted to 0.2 to 5.9% by weight.

[Claim 8]

The method of claim 3, wherein

Air flow injected for the catalyst regeneration of step 2 is a method for producing light olefins, characterized in that the average coke content of the regenerated catalyst is adjusted to 0.5-4.6 increase ¾>.

[Claim 9]

The method of claim 3

The temperature of the reactor is 300-600 ^° C, the circulation rate of the catalyst in the reaction vessel is 1-100 kg / h, the space velocity of methanol injected into the reactor is 0.5-300 h ᅳ ¹ and the temperature of the catalyst regenerator Is 500-700 V, and the air flow rate injected for catalyst regeneration is 5 -.50 1 / min.

[Claim 10]-preparing light olefins by contacting methane with a supercatalyst in a circulating fluidized bed reactor equipped with a catalyst regeneration unit and a product separation unit (step 1);

Monitoring the selectivity of the dimetal ether, intermediate of step 1 (step

2); And

Injecting air for regeneration of the catalyst by separating the used catalyst of step 1, but adjusting the flow rate of the injected air according to the selectivity of the dimethyl ether of step 2 System (step 3); The method of improving the yield of hard olepin.